JPH0554658B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION The present invention provides novel xanthene compounds and their use in, for example, light-screening.
screening) for use as a dye in photographic products and methods. DESCRIPTION OF THE PRIOR ART It is known that photographic films, particularly multicolor films, can and generally do vary from production lot to production lot, and great efforts are expended to "recreate" previous films. Manufacturers of multicolor photographic film have developed a number of methods to minimize the effects of the manufacturing process on inevitable changes in the final multicolor image. These changes primarily result in a shift in color balance, which is reflected in a mismatch of the DlogE curves for red, green, and blue exposures. Although the equipment used for multicolor films is highly accurate, variations in the intended coverage of silver halide and/or dye imaging material occur. Repeated manufacturing of silver halide emulsions can also, and generally does, result in changes in their photographic response. Each layer may individually dry to a slightly different extent. Since the film is stored and aged for a period of time after application, there is an opportunity for post-application sensitometric changes to occur until they are constant prior to marketing.
If the film is designed to be developed by a photofinishing professional or in a darkroom, the processing of exposed multicolor film must occur within very narrow limits, typically within ±0.5 degrees of the specified temperature. adjusted to minimize film-to-film sensitometric variation. If the multicolor film is negative-acting, the opportunity to adjust the sensitometry occurs during printing of the desired final positive image, and during this operation print exposure using appropriate color filters can be carried out. The basic causes of sensitometric variation described above are also present in multicolor diffusion transfer films, with the added problem that the sensitometric properties are essentially fixed once the film is shipped. Practically speaking, the control opportunities that darkroom processing has provided are not available to users of self-developing films. While professional and seasoned amateur photographers are well skilled at using color correction filters to "rebalance" color balance in small areas, the average film user may not be able to use such additional It just confuses the operation. The use of optical screening dyes in photographic elements is well known. Such dyes may be present in the light-sensitive emulsion layer (single or multilayer) or in a layer coated on top of one or more light-sensitive emulsion layers, or in two different color sensitizers. can be incorporated between emulsion layers that are present in the emulsion layer, thus modifying the optical recording in the emulsion layer or controlling the spectral composition of the light that falls on the underlying light-sensitive layer, or ) can also be incorporated as an antihalation dye into the non-photosensitive layer located on either side of the support. In addition to having the necessary spectral absorption properties for their intended purpose, dyes used for these purposes should be photographically inert. That is, they should not have any deleterious effect on the properties of the light-sensitive emulsion layer (single or multilayer), and they may be bleached or removed during photographic processing to form a processed photographic element. It should not leave any stains. In photographic methods where the dye is removed by dissolving it in the processing solution, the dye is also removed once the dye is decolorized to avoid contamination of the processing solution and to prevent staining with residual dye in the processed light-sensitive element. Usually preferred. Although various types of dyes have been proposed for use in antihalation and color correction filter layers, all previously used dyes have not been satisfactory. Certain groups of dyes have tended to reduce sensitivity, or tend to fog, or have other deleterious effects on the photosensitive material. However, a major drawback of the dyes hitherto used is that they tend to stain due to incomplete bleaching or to revert somewhat from the bleached form to the originally colored form. For example, some dyes rely on bleaching, that is, the presence of a reactive agent such as a sulfite for decolorization, which reduces their color over time unless the dye is removed from the light-sensitive material during or after processing. It may be reproduced with. Among the types of photoscreening dyes previously used are triarylmethane and xanthene compounds. For example US Patent No. 1879537
No. 1994876; No. 2350090; and No. 2350090;
No. 3005711 discloses the use of fuchsone type dyes in antihalation layers, and U.S. Pat.
No. 3,615,548 discloses metal chelates of Faxon dyes as antihalation dyes. These and other types of triarylmethane dyes have one or more of the disadvantages mentioned above, especially at the PH normally encountered during post-bleach processing and in the final product. It was difficult to maintain the decolorized state. Xanthene compounds are used in antihalation layers that are removed after photographic processing. For example, U.S. Pat. No. 2,182,794; U.S. Pat. No. 2,203,767; and U.S. Pat. No. 2,203,768 disclose rhodamine in certain antihalation layers that are removed during processing in an acid bath or a plain water wash bath, depending on the solubility characteristics of the particular layer. Discloses the use of dyes. U.S. Patent Nos. 4,258,118 and 4,304,834 are 9
expression in position (In the formula, X is

[expression] or

A group of 3,6-disubstituted xanthene compounds having a substituted phenyl group of the formula: where R' is alkyl and Y is an electron-withdrawing group is disclosed. In these compounds, the X group undergoes an irreversible cleavage reaction in a base to generate an irreversible group at the central carbon atom, producing a new colorless closed ring compound. As disclosed and claimed in these patents, these compounds have the ability to completely decolorize and produce substantially inert products that remain colorless over a wide PH range. Because it changes irreversibly,
It is useful as a photographic optical screening dye, offering advantages over conventional optical screening dyes. Structural formula The xanthene compound (wherein R is H or _-COCH3 ) was prepared by Beilstein's Handbuch der
It is disclosed in Organischen Chemie, Vol. 27, p. 534. These compounds are produced by condensing n-diethylaminophenol with saccharin at a temperature of 165°C.
It is synthesized by forming a compound in which R is H, which is then heated to boiling with acetic anhydride to form the N-acylated derivative. As reported in the same literature, the solution of this N-acetyl compound is not decolorized by boiling, unlike the solution of N-unsubstituted compound (R=H), and this acetyl group is dissolved in alcoholic sodium hydroxide. It is desorbed only after boiling for a long time. Furthermore, for the N-unsubstituted compound, it was found that the compound is colorless at alkaline PH, faintly colored at neutral, and becomes more intensely colored as the PH decreases. SUMMARY OF THE INVENTION The present invention relates to a new class of xanthene compounds that are useful as photographic optical screening dyes. This compound, like the xanthene compounds of US Pat. Nos. 4,258,118 and 4,304,834, does not exhibit the drawbacks associated with dyes previously used for this purpose. The dye according to the invention is from 400 to
It is an effective absorber of radiation within a defined range within the visible range of 700 nm and can be incorporated into gelatin or other processing composition permeable colloidal binders and decolorized at alkaline PH to produce a colorless product. Because of its ability to completely and irreversibly decolorize in base without the need for additional reactants such as sulfites in the "bleach" reaction, and the novel colorless products produced by irreversible cleavage,
Since it remains colorless in aqueous solutions from PH14 to below neutral, this cleavage product can be retained in photographic elements without the possibility of reproducing color over time. In addition to being non-staining, these compounds are usually substantially inert to the light-sensitive material and are therefore incorporated into layers adjacent to the silver halide emulsion layer or directly into the emulsion layer. can be incorporated without any deleterious effect on the properties of the emulsion. In addition to the above advantages, the rate at which the dyes according to the invention decolorize at a given PH can be easily adjusted to suit the requirements of a given photographic system. Therefore, the main object of the present invention is to provide new xanthene compounds. Another object of this invention is to provide xanthene compounds useful as optical screening dyes in photographic products and methods. Yet another object of the invention is to provide photographic articles and methods using these compounds. Other objects of the invention are, in part, self-evident:
One part will be clear from the description below. Accordingly, the invention is illustrated by the following detailed description of the steps and their relationships and methods involving one or more of such steps in relation to one another, and the scope of its use is as defined by the claims. It includes products and composites having the characteristics, properties and elemental relationships indicated. For a better understanding of the nature and objects of the invention, the following detailed description should be considered in conjunction with the accompanying drawings. FIG. 1 shows a diagrammatically enlarged cross-section of a diffusion transfer film unit incorporating the xanthene dyes of the present invention as a bleachable antihalation dye layer; FIG. Figure 3 shows a schematically enlarged cross section of another diffusion transfer film unit incorporated into the image receiving layer as a color correcting filter dye; and Figure 3 shows the change in Hammett sigma value for substituent This is a graph based on the Hammett equation, which has a linear relationship with the hydrolysis rate of the compound in a 0.25N potassium hydroxide solution. DESCRIPTION OF THE INVENTION Specifically, the compounds provided by the present invention have the formula (In the formula, each R ¹ is the same and a group

[expression] and

[Formula], R ² is alkyl, R ³ is an electron-withdrawing group in the ortho, meta or para position to the N atom, and R ⁴ is hydrogen, alkyl or N
is an electron-withdrawing group in ortho, meta or para position to the atom, R ⁵ is alkyl, X
is hydrogen, an electron-withdrawing group or an electron-donating group, and A is an anion). The term "electron-withdrawing group" means a group with a positive sigma value, as defined by Hammett's equation, and the term "electron-donating group" means a group with a negative sigma value, as defined by Hammett's equation. means a group having a sigma value. Representative R ² , R ⁴ and R ⁵ groups include alkyl groups having 1 to 4 carbon atoms, such as methyl,
Ethyl, n-propyl, n-butyl and s-butyl, with methyl being preferred. Any electron-withdrawing group or any electron-donating group can be used for X, and any electron-withdrawing group can be used for R ³ and R ⁴ . Representative electron-withdrawing groups that can be used for R ³ , R ⁴ and X include -CN, -NO ₂ , -SO ₂ CH ₃ ;-
SO ₂ CH ₂ CH ₃ ,

【formula】

[Formula] −CHO, −COOH, −COOCH ₃ , −COOC ₂ H ₅ , −COCH ₃ ,

[Formula] −CO−NH ₂ , −SO ₂ (CH ₂ ) ₃ CO ₂ H, −OCOCH ₃ , −SO ₂ N(CH ₃ ) ₂ , −
SO ₂ NHCH ₂ CH ₂ OH, −SO ₂ N(CH ₂ CH ₂ OH) ₂ , −
Includes _SO2NH2 , _-CF3 , Br _and Cl. When X is not an electron-withdrawing group but an electron-donating group,
Typical electron-donating groups that can be used for X are -
_CH3 , _-C2H5 , _-OCH3 , -N( _{CH3 ) 2} , _{-OC2H5 and}

[Formula] is included. The sigma values for these and other groups are found in Lalg′s Handbook of
Chemistry, John A. Dean, McGraw-Hill,
New York, 1972, pages 3-132 to 3-137. The anion associated with the xanthene compound of the present invention, that is, A in the above formula 2, is a simple anion, such as tosylate, sulfate, nitrate,
perchlorate, methanesulfonate, methane hydrogen disulfonate, m-benzene hydrogen disulfonate, acetate, oxalate or halide (e.g. chloride, bromide or iodide)
It can be either. It is to be understood that other resonance forms of the compounds of the invention are also included in the formula. As mentioned above, the compounds of the present invention are initially colored, that is, they are capable of absorbing visible light;
Then, at alkaline pH, it undergoes an irreversible cleavage reaction with a base, that is, a hydrolysis reaction, and is converted into a free product. The colorless product produced is a compound different from the colored compound, and is a new compound that does not revert to the colored compound due to a change in pH. In particular, the benzoyl sulfonamide group substituted on the phenyl moiety undergoes an irreversible cleavage reaction in an alkaline solution that is completed within a given time at a given alkaline pH to form a novel colorless compound, i.e., a cyclic sulfonamide compound ( A = Cl ^- ) is generated. This can be shown by the following equation: It is clear that the by-products formed during hydrolysis of the benzoylsulfonamide groups are also colorless. This hydrolysis reaction proceeds at a faster rate the higher the pH, so the compound of interest is processed at a pH of about 10 for at least the time required to decolorize to the corresponding ring-closure product.
Particularly suitable for use in photographic methods that are more than maintained. As mentioned above, the rate at which the dyes of the present invention decolorize at a given PH can be easily adjusted according to the requirements of a particular photographic process. This is achieved by appropriate selection of the X group. Compared to when X is H, the rate of hydrolysis can be reduced by using an electron-donating group as X, and the rate of hydrolysis can be increased by using an electron-withdrawing group as X. . The particular rate of decolorization required in a given photographic system and the particular X groups required to provide the desired rate can be determined experimentally. Also, as mentioned above, the cyclic sulfonamide produced as a result of alkaline hydrolysis remains colorless until neutral or below. Since the final PH, i.e. the PH ultimately reached after processing, can vary for different photographic systems, the combined electron-withdrawing effect of R ³ and R ⁴ groups confers a cyclic sulfonamide that remains colorless at a specified final PH. should be sufficient. For example, at a low PH of 4-5, the electron-withdrawing group(s) chosen will have a larger negative sigma value than required at a PH of 6. To ensure that the cyclic sulfonamide cleavage product remains colorless at a particular pH below neutrality, the specific groups required to tune the electron-withdrawing effect can be easily determined experimentally for a given photographic system. You can decide. The xanthene dye of the present invention is disclosed in the above-mentioned U.S. Pat.
It can be produced by conventional methods using the methods described in Nos. 4,258,118 and 4,304,834. For example, the dyes of the invention can be synthesized by the following method: (a) Formula (In the formula, R ¹ and R ⁵ have the same meanings as above)
by reacting the cyclic sulfonamide with a reducing agent,
formula (In the formula, R ¹ and R ⁵ have the same meanings as above)
(b) converting said reduction product to the corresponding benzoyl chloride [

React with [formula] to form the formula (In the formula, R ¹ , R ⁵ and X have the above meanings)
and (c) oxidizing said leuco dye precursor using preferably o-chloranyl or p-chloranil as an oxidizing agent, and then liberating the dye from its chloranil complex with an acid. , producing a dye product. The raw material used in step (a) is sulfonefluorescene dichloride with isodrine or the formula It can be synthesized by reacting with a substituted aniline (wherein R ³ and R ⁴ have the above-mentioned meanings) to produce the corresponding 3,6-disubstituted sulfonefluorescene. It is preferred that both of the two chloro groups of the sulfonefluorescene dichloride be substituted stepwise rather than in a single step. 3,6
-When the substituted compound is derived from aniline,
The compound is reacted with an alkylating agent to form the 3,6
- Substituting the N atom of the anilino substituent with an alkyl group. The 3,6-disubstituted compound is then treated with phosphorous pentachloride or thionyl chloride to produce the corresponding sulfonyl chloride, which is then converted to the cyclic sulfonamide with ammonia. If benzoyl chloride is not commercially available, a compound with the desired X group can be derived to produce the acylating agent used in step (b) above. The following examples further illustrate the invention:
It is not intended to limit the scope of the invention. Example 1 formula Production of a compound having: (a) formula 10.0 g of the compound having the formula are dissolved in a solution of 60 ml of N-methylpyrrolidinone and 15 ml of trifluoroacetic acid and then heated to 60 DEG C. under a nitrogen atmosphere.
Aene powder (50 g) is added all at once and the reaction mixture is stirred at 65° C. for 0.5 h. The pale gray reaction mixture is poured into a solution of 500 ml methanol/40 ml concentrated hydrochloric acid and stirred overnight. The solid was collected, washed well with methanol, then dried in vacuo, and the formula 10.8 g of intermediate having . (b) 9.0 g of the intermediate produced in step (a) was mixed with 200 g of pyridine.
A suspension of 11.4 g of p-nitrobenzoyl chloride in ml is added at 5° C. and then stirred at room temperature.
After 5 hours, TLC shows the reaction to be approximately 50% complete. An additional 4.1 g of p-nitrobenzoyl chloride is added and the reaction mixture is stirred over the weekend. The reaction mixture was then poured into 1600 ml of water, the resulting precipitate was collected and the formula to produce a dye precursor having a (c) Dissolve the dye precursor of step (b) in 100 ml of a solution of 80% methyl ethyl ketone/20% methanol.
Add 7.4 g of p-chloranil to this solution. 2
After refluxing for an hour, TLC showed the reaction was essentially complete. The solvent is evaporated and the solid is refluxed in 200 ml of toluene for 2 hours. The solid containing the chloranil complex of the dye product is then dissolved in 300 ml of dichloromethane and 10 ml of methanol and saturated with anhydrous HCl for 20 minutes. The solution was stirred for 1 hour and the solvent was evaporated, leaving 19.5 g of blue solid.
get. The title compound is isolated using high pressure liquid chromatography and 5-6% methanol/dichloromethane as the eluent. Example 2 formula Manufacture of a compound having Step (a) is carried out in the same manner as described in Example 1, with the formula to produce an intermediate having the following. (b) The intermediate (0.78 g) produced in step (a) was cooled (5
°C) Add to 20 ml of pyridine. Partial dissolution occurs and then solids form. This suspension contains p
-1.0 g of dimethylaminobenzoyl chloride is added and the reaction mixture is stirred at room temperature over the weekend. Add another 0.4g of benzoyl chloride,
The reaction mixture is stirred for 6 hours. The reaction mixture is then filtered and the filtrate is precipitated into 200 ml of water. The pale blue precipitate was collected, air-dried, washed with methanol, air-dried again, and the formula 1.3 g of dye precursor having . (c) Dissolve the dye precursor (1.3 g) produced in step (b) in 25 ml of 20% methanol in methyl ethyl ketone. Add 20 ml of dichloromethane to complete dissolution. 0.87 g of p-chloranil is added to this solution and the mixture is refluxed for 1.5 hours. The reaction mixture is refluxed with toluene to remove impurities and excess chloranil. The solid is then dissolved in dichloromethane and anhydrous HCl is bubbled into the solution for 10 minutes. After stirring for 1 hour, the solvent is removed by evaporation and the blue solid is chromatographed by high pressure liquid chromatography to yield 0.17 g of the title compound. Example 3 formula Manufacture of a compound having (a) Eq. 1.5 g of the compound having the formula (R ₁ has the same meaning as above) are dissolved in 40 ml of acetic acid and heated to 60° C. under nitrogen atmosphere. Add a total of 0.75g of Aene powder in three parts over a period of 0.5 hours. The reaction mixture is heated at 60° C. for 2 hours, filtered and the filtrate is added to 500 ml of water to form a precipitate. The precipitate is collected and air-dried to obtain 1.5 g of the following intermediate as a pale pink solid: (wherein R ₁ has the same meaning as above). (b) Dissolve the intermediate (0.2 g) produced in step (a) in 20 ml of pyridine and cool to 0° to -5°C. p
-Add chlorobenzoyl chloride (0.4g),
The reaction mixture is stirred at 5° C. for 1 hour and then allowed to warm to room temperature. After stirring for 4 hours at room temperature, TLC shows some unreacted intermediate. A few more drops of benzoyl chloride are added and the reaction mixture is stirred for an additional hour. The reaction mixture was then poured into water, the precipitate was collected and air-dried, and the dye precursor of formula 0.6 was added as a white solid.
Generate g: (wherein R ₁ has the same meaning as above). (c) Dissolve the dye precursor (0.6 g) produced in step (b) in 25 ml of dichloromethane and add p-chloranil.
Add 0.28g. The reaction mixture was stirred at room temperature;
After 2 hours, TLC shows the reaction to be approximately 50% complete. The mixture is stirred over the weekend and then saturated with anhydrous HCl for 0.5 h. The reaction mixture is poured into ether and the ultrafine precipitate is separated by centrifugation and dried to give 0.43 g of solid. This solid was chromatographed on silica gel using 4-5% methanol/dichloromethane as eluent to yield the title compound 0.32
get g. Example 4 formula Manufacture of a compound having The title compound (0.285 g) is prepared in a manner similar to that described in Example 3 above, except that benzoyl chloride is used in step (b). Example 5 and 6 Formula Example 5 Example 6 production of compounds. The title compound is prepared in the same manner as described in Example 3 above, except that p-nitrobenzoyl chloride is used in step (b). Example 7 Formula Manufacture of a compound having (a) Equation 0.4 g of the compound (wherein R ₂ has the same meaning as above) and 0.21 g of p-methoxybenzoyl chloride in 20 ml of anhydrous pyridine were cooled (5°C).
Add to solution. The reaction mixture is stirred in an ice bath for 1 hour and kept at about -5°C for 5 hours. The reaction mixture was added to 400 ml of water to cause precipitation, the purple solid was collected, air dried and chromatographed on a medium pressure column of silica gel using 2% methanol/dichloromethane as eluent;
formula produce an intermediate with (b) Dissolve the intermediate produced in step (a) (0.5 g) in 10 ml of dimethyl sulfoxide and add 0.04 g of 60% sodium hydroxide along with 0.5 ml of methyl iodide. The reaction mixture was heated to 50°-60°C for 2 hours,
Stir overnight at room temperature. An additional 0.04g
Add 60% sodium hydroxide along with 1 ml of methyl iodide and heat at 50° C. for 7 hours, then after 3 hours add another 1 ml of methyl iodide. TLC
After taking a sample, the reaction mixture is again left overnight with additional methyl iodide. The reaction mixture is then poured into water and the precipitate is collected and air dried to obtain 0.46 g of product. The product was chromatographed on a medium pressure silica gel column using 5% methanol/dichloromethane as eluent to yield the title compound.
Obtain 0.27g. The following intermediates are also prepared by reducing the corresponding cyclic sulfonamides as described in the previous examples. using the method described above to react these intermediates with benzoyl chloride to produce a dye precursor;
It is clear that the dye product can then be oxidized and isolated. As mentioned above, the dye of the present invention can be completely and irreversibly decolorized in a base by undergoing an irreversible cleavage reaction at a given pH and within a given time;
It has the ability to produce a new colorless compound that remains colorless at the PH that typically increases during post-"bleaching" processing, and thus this new compound has the potential to reproduce color even over time. It can be retained in a photographic film unit, such as a developed photosensitive element, without attachment. Typically, the dye will be selected for use as an antihalation dye, for example in a non-light-sensitive layer located intermediate the light-sensitive silver halide emulsion layer and the support. The dye may also be selected for use as a color correction filter dye when absorption of light within a particular wavelength range during exposure is desired to achieve a predetermined color balance. Specific film units in which the dyes of the invention can be advantageously used as antihalation dyes are described, for example, in GB 1,482,156. These film units include, in the order through which the incident light passes, an additive multicolor screen, a light-sensitive silver halide emulsion layer, an antihalation layer which may contain a selected compound therein, and preferably an image-receiving layer. do. As described in this patent, exposure of the silver halide layer is accomplished by using an optical filter element that selectively transmits predetermined regions of incident radiation, such as red, green, and blue light to the underlying light-sensitive silver halide layer. This is done through a screen with a Upon photographic processing with aqueous alkaline processing compositions, soluble silver complexes are transferred and deposited by diffusion into the stacked image-receiving layers as a function of the degree of exposure of the silver halide behind each filter element. The silver image thus formed can serve to control the amount of light passing through the filter element in the opposite direction during projection through the transparent support. In a preferred embodiment, the image-receiving layer is intermediate the light-sensitive silver halide emulsion layer and the additive multicolor screen and remains in place as part of the integral film unit before, during and after formation of the image. ing. The antihalation dye is disposed in the processing composition transparent layer adjacent to the photosensitive layer on the opposite side of the screen and serves to prevent reflection or back scattering of incident light passing through the photosensitive layer. As noted above, the dyes of the present invention can also be used in photographic film units containing multilayer, multicolor photosensitive elements employing blue, green, and red photosensitive silver halide layers, particularly image-receiving layers carrying color transfer images after processing. It is also useful as a color correcting filter dye in an integrated negative-positive diffusion transfer film unit that does not separate from the developed photosensitive layer and holds both parts together as a permanent laminate. Part of the laminate includes a layer of light-reflecting material, preferably titanium dioxide, located between the image-receiving layer and the developed photosensitive layer (monolayer or multilayer). A light reflective layer separating the image-bearing component and the photosensitive component provides a background for the transferred image and masks the developed photosensitive layer (single layer or multilayer). In addition to these layers, the laminate typically has dimensions such that at least one of the layers is transparent and the resulting transferred image is made visible by reflection against the background provided by the light-reflective layer. Includes a stable outer layer or support. Representative examples of patents disclosing such film units include U.S. Pat. No. 2,983,606, issued March 9, 1961 to Howard G. Rogers;
U.S. Patent Nos. 3,415,644, 3,415,645 and 3,145,646 issued December 10, 1968 to Edwin H. Land, to Howard G. Rogers.
U.S. Patent issued July 20, 1971
3594164 and 3594165, and Edwin
There is US Pat. No. 3,647,437 issued March 7, 1972 to H.Land. U.S. Patent No. 1, issued May 11, 1982 to Edwin H. Land.
No. 4,329,411 discloses a multicolor diffusion transfer film unit having a layer of a dye, preferably a dye decolorizable by a processing composition, through which exposure is effected and the dye layer thus arranged to act as a color correction filter. ing. For convenience, the description of this patent is specifically incorporated herein. Whether used as antihalation dyes or as color-correcting filter dyes or in other conventional photographic light screening applications, the dyes of the present invention, when placed in a processing composition permeable layer, bind aqueous alkaline processing compositions and colored dye compounds. The color is completely and irreversibly decolored by contact for the time necessary to convert it to the new colorless closed ring compound.
The time required for decolorization, i.e., the time required to convert a colored compound to a colorless product by an irreversible cleavage reaction, can be measured at any given alkaline PH, and for the selected decolorization time, the time required to contact the colored filter dye and the contact The PH of the treatment composition that remains should be at least as high as the predetermined height to obtain the selected bleaching time. The dyes of this invention can be incorporated into the appropriate layers of a photographic film unit using any of the techniques known in the art. For example, the selected compound is dissolved in a suitable solvent and then dispersed in a coating solution containing a hydrophilic colloidal binder, such as gelatin, optionally in the presence of a wetting agent, and the resulting coating solution is applied as the desired layer. applied, for example, on a transparent support to form an antihalation layer, or on the outermost photosensitive layer of a multilayer multicolor photosensitive element,
A color correction filter layer can be formed through which the exposure takes place. The concentration of the compound in the layer is
This filter layer will vary depending on the product in which it is used and can be determined experimentally to provide the optical density required for a particular application. It is clear that the dyes of the invention can be used in combination with each other and with other types of dyes conventionally used in antihalation, color correction and other filter layers. FIG. 1 illustrates one embodiment of the invention, on one surface of which a plurality of primary red filter elements, a plurality of primary green filter elements and a plurality of blue filter elements are arranged in order in a substantially simple manner. On one side, arranged in a geometrically repeating distribution in side-by-side relationship, an additive multicolor screen 3, a non-photosensitive layer 5 carrying silver precipitation nuclei, a photosensitive layer 7 containing silver halide crystals, and a book. 1 shows an enlarged cross-section of an integrated diffusion transfer film unit comprising a transparent film base or support 1 carrying an antihalation layer 9 containing one or more of the photoscreening dyes of the invention. As described in said GB 1482156, the light absorption of the antihalation layer in such film units can vary over a relatively wide range, but typically the antihalation layer has a
It has a transmission density range of 0.4-1.4. Preferably,
This transmission density is greater than 0.6 and thus has a sufficient density, i.e., light absorption, so that when multiple film units are used stacked during exposure, the antihalation layer also prevents exposure of the film units below it. be able to do so. For color correction purposes, to determine the appropriate light absorption capacity for cyan, magenta, and yellow, use a conventional "color correction" filter in front of the camera lens to determine the appropriate light absorption capacity for the type and amount of filtration desired to be applied. It can be used in a conventional manner as a convenient method. A layer containing a suitable color correcting dye(s) in a substantial concentration can thus be applied as a layer through which exposure is effected. Multicolor diffusion transfer images can be obtained using various arrangements of image-receiving layers and silver halide emulsions. These layers can therefore be supported by customary supports for lamination after exposure. A particularly advantageous film structure is shown in U.S. Pat. No. 3,415,644, in which the necessary layers are in stacked relationship before and during processing, and which remain as a permanent stack after processing and imaging. They are held in a stacked relationship. Such film units typically include a transparent outer layer or support through which exposure is made and the final polychrome image visible, and another outer layer or support (which is opaque) carrying at least a light-sensitive layer. ). The supports or sheet-like elements can simply be held in stacked relation, for example by binding tape around the edges, but the elements can also be stacked together before exposure. This pre-lamination offers many benefits both in terms of manufacturing and exposure. After exposure, each element is delaminated by the distribution of a liquid treatment composition which, upon solidification, bonds the elements together to form the desired permanent laminate. A method of forming a pre-laminated film unit in which two types of elements are temporarily laminated before exposure is described, for example, by Albert J. Bachelder and Frederick J. Binda.
U.S. Patent No. 28, 1972, issued March 28, 1972 for
No. 3625231 to Edwin H. Land, March 28, 1972.
U.S. Patent No. 3,652,282, issued on
No. 3,793,023 issued February 19, 1974 to Edwin H. Land. A more detailed explanation of this aspect of the invention can be facilitated by reference to FIG.
FIG. 2 illustrates a diffusion transfer film unit suitable for producing integrated negative-positive reflection prints and employing a dye developer as the image dye. FIG. 2 shows a diffusion transfer film unit including a photosensitive element or component 2, a rupturable container 30, and an image receiving element or component 4. FIG. The photosensitive element 2 includes, in order, a cyan dye developer layer 12, a red-sensitive silver halide emulsion layer 14, an intermediate layer 16, a magenta dye developer layer 18, and a green-sensitive silver halide emulsion layer 2.
0, an opaque support 10 carrying an intermediate layer 22, a yellow dye developer layer 24, a blue-sensitive silver halide emulsion layer 26 and an auxiliary layer 28. The positive or image-receiving element 4 is comprised of a transparent support 40 carrying, in order, a polymeric acid layer 42, a timing layer 44, and an image-receiving layer 46 in which the bleachable photoscreening dye of the present invention is dispersed as a color-correcting filter dye. Contains. The two elements are held in stacked registration, for example by a bonding tape (not shown), and exposure of the silver halide emulsion layer is through an image-receiving layer containing a bleachable dye. The rupturable container 30 contains the treatment composition and is arranged so that when ruptured, the treatment composition is distributed between the stacked elements 2 and 4. By including a light-reflecting pigment, preferably titanium dioxide, in the treatment composition, the image-receiving layer 46
It is possible to provide a light-reflective layer that allows a transferred image formed on the surface to be seen against the background of the transferred image. The developed photosensitive layer is masked from view by this light reflective layer and can remain with the image receiving layer 46 as part of the permanent stack. The rupturable container is covered by U.S. Patent No.
It is of the type shown in No. 2543181,
It is located adjacent to the long edge of the film unit. When processing a film unit, the film unit applies a compressive pressure to the rupturable container 30 between a pair of pressurizing means whose liquid contents are released between the photosensitive element 2 and the image receiving element 4. and distributed between the sheets towards their edges to produce a substantially uniform layer of defined thickness, at least as wide as the image area. To ensure that there is sufficient processing liquid to form a layer of the required area and thickness between the sheets, excess processing liquid is provided in a container 30 for collecting and retaining the excess processing liquid effluent. Prepare capture means (not shown). Details of the various layers of this and the film units of FIG. 1 can be found in the patents and patent applications cited above.
I will not repeat it here. Processing of a film unit of the type disclosed in FIG. 2 begins by distributing a processing composition between predetermined layers of the film unit. In the exposed and developed areas, the dye developer becomes immobilized as a result of development. In the unexposed and undeveloped areas, the dye developer is unreacted and diffusive, thus leaving the processing composition with a diffusible unoxidized dye developer as a function of the point-to-point degree of exposure of the silver halide layer. An imagewise distribution of the agent is formed. The desired transferred image is obtained by diffusively transferring at least a portion of this imagewise distribution of unoxidized dye developer to the image receiving layer. In an exemplary embodiment, the PH of the photographic system is adjusted to a PH in which the unoxidized dye developer is substantially insoluble and non-diffusible by neutralizing the alkali after a predetermined time interval in accordance with the teachings of the aforementioned U.S. Pat. No. 3,615,644. Regulate and reduce by reducing its alkalinity to . As will be readily acknowledged, the details of such methods do not form part of the present invention and are well known; reference may be made to the aforementioned U.S. patents for a more detailed description of such methods. . Polychromatic images can be obtained by providing the required number of differently exposed silver halide emulsions; such silver halide emulsions are for the most part usually formed by coating each layer in a stacked relationship. can get. The film unit that attempts to form a multicolor image is
a selection of two or more species, each having in combination therein a suitable image dye-providing substance which provides an image dye with spectral absorption characteristics that are substantially complementary to the light to which the silver halide in combination is exposed; It includes a silver halide layer that has been sensitized. The most conventional negative components for the formation of multicolor images have a "tripack" structure, with blue-, green-, and red-sensitive materials having yellow, magenta, and cyan image dye-providing substances, respectively, in combination therein in the same or adjacent layers. Contains a silver halide layer. If desired, interlayers or spacer layers can be used between each silver halide layer and the associated image dye-providing material or between other layers. This general type of integrated multicolor photosensitive element was developed by Edwin H.Land and Howard
No. 3,345,163 issued Oct. 3, 1967 to G. Rogers, as well as in FIG. 9 of the aforementioned U.S. patents, such as the aforementioned U.S. Pat. No. 2,983,606. Many variations of the structure described above in connection with FIG. 2 will themselves readily occur to those skilled in the art. For example, U.S. Patent No. 17, 1961, issued to Edwin H. Land.
Screen-type negatives can be used in place of multicolor, multilayer negatives, as illustrated in US Pat. Image dye-providing materials that can be used in such methods generally have one of the following characteristics: (1) are initially soluble or diffusible in the processing composition, but become selective in an imagewise pattern as a result of development; or (2) initially insoluble or non-diffusible in the processing composition, but becomes selectively diffusive in an imagewise pattern as a result of development, or a diffusible product I will provide a. These materials can be complete dyes or dye intermediates, such as color couplers. The necessary difference in mobility or solubility is
For example, it can be obtained by a chemical reaction such as a redox reaction or a coupling reaction. Examples of initially soluble or diffusible materials and their use in color diffusion transfer include:
For example, US Patent No. 2968554, US Patent No. 2983606,
Same No. 3087817, Same No. 3185567, Same No. 3230082,
Examples include those described in the same No. 3345163 and the same No. 3443943. Examples of initially non-diffusible materials and their use in color diffusion transfer include U.S. Pat.
No. 3443939, No. 3443940, No. 3443940, No. 3443939, No. 3443940, No.
3227550, 3227552, and 4076529
You can list the items listed in the issue. A large variety of image dye-providing materials and film units useful therein are also disclosed in the aforementioned U.S. Pat. No. 3,647,437, which reference may be made to. It should be understood that "direct positive" silver halide emulsions can also be used depending on the particular image dye-providing material used and whether a positive or negative color transfer image is desired. It is. A suitable opacifying system for inclusion in the processing composition for processing outside the camera is described in the aforementioned US Pat. No. 3,647,437 and has dispersed inorganic light-reflecting pigments. The system also includes at least one light absorber, i.e. an optical filter agent,
When the processing composition is applied, the photosensitive silver halide has an optical transmission density of greater than about 6.0 density units for incident radiation and an optical density of less than about 1.0 density units for incident visible radiation. It is contained in an effective concentration to provide a layer exhibiting reflection density, and has a pH equal to or higher than the pKa value of the optical filter agent. A light-reflecting pigment used to mask the light-sensitive layer and provide a background for viewing the color transfer image formed in the image-receiving layer, in lieu of the presence of a light-reflecting pigment in the processing composition. They can also be present in whole or in part as ready-made layers in film units from the beginning. Examples of such off-the-shelf layers include the 1971 10 for Edwin H.Land, respectively.
U.S. Patent No. 3,615,421, issued Nov. 26, 1971;
Examples include those described in No. 3620724.
Reflective agents each 1972 to Edwin H.Land
As disclosed in U.S. Patent Nos. 3,647,434 and 3,647,435, issued March 7,
Generally can be generated on the fly. Dye developer (or other image dye-providing substance)
are preferably selected for their ability to provide colors useful in the practice of subtractive color photography;
It is preferable to select from the cyan, magenta and yellow. These materials can be incorporated into each silver halide emulsion or, in a preferred embodiment, in a separate layer behind each silver halide emulsion. The dye developer is thus coated, for example, behind each silver halide emulsion or applied as a layer. Such a layer of dye developer may be made of a film-forming natural or synthetic polymer, such as gelatin, polyvinyl alcohol, etc., at a concentration calculated to provide the desired dye developer coverage per unit area. It can be applied by using a coating solution containing a dye developer dispersed in a material suitable for transmission of the processing composition. As mentioned above, the dye developer is a compound having a chromophore system of a dye and a silver halide developable functional group. The term "silver halide developable functional group" means a group suitable for developing exposed silver halide. A preferred silver halide developable functional group is a hydroquinonyl group. Other suitable developable functional groups include ortho-dihydroxyphenyl and ortho- and para-amino substituted hydroxyphenyl groups. Generally, the developable functional group has a benzenoid developable functional group, ie, an aromatic developable group that upon oxidation produces a quinonoid or quinone material. The image receiving layer can contain one of the materials known in the art such as polyvinyl alcohol, gelatin, etc. It may also contain suitable auxiliaries for mordanting or otherwise fixing the transferred image dye(s). A preferred material is U.S. Pat. No. 3,148,061
polyvinyl alcohol or gelatin containing a dye mordant as described in US Pat. No. 3,756,814;
Includes graft copolymers containing vinylpyridine. In the various color diffusion transfer systems described above and using aqueous alkaline processing solutions, the peripheral PH is lowered after substantial dye transfer to increase image stability and/or the image dye is diffusive. It is well known to use acid-reactive agents in the layers of film units to adjust the PH from an initial PH to a second (lower) PH at which these are non-diffusible. For example, the above-mentioned US Pat. No. 3,415,644
A system is disclosed in which the desired PH reduction can be achieved by applying a polymeric acid layer adjacent to the dyeable layer. These polymeric acids contain alkali metals and
Or it can be a polymer containing acid groups capable of forming salts with organic bases, such as carboxylic and sulfonic acid groups, or potentially acid-forming groups such as anhydrides or lactones. Acid polymers containing free carboxyl groups are preferred. Alternatively, an acid-reactive agent can be used as described in 1971 by Edwin H.
It can also be present in the layer adjacent to the silver halide furthest from the image-receiving layer, as disclosed in U.S. Pat. Another method for providing acid-reactive agents
One system is disclosed in US Pat. No. 3,576,625, issued April 27, 1971 to Edwin H. Land. An inert interlayer or spacer layer may be present between the polymeric acid layer and the dyeable layer to control or time the PH reduction to eliminate premature processing and interference from processing. I can,
This is generally preferred. A spacer or "timing" layer suitable for this purpose is particularly described in U.S. Pat.
No. 3362819, No. 3419389, No. 3421893, No. 3455686, and No. 3575701. The acid layer and its combined spacer layer can be used in positive parts using systems in which the dyeable layer and the photosensitive layer are carried on separate supports, e.g. or in combination with a dyeable layer in an integral film unit, e.g. on the opposite side of the dyeable layer from the negative parts, as described e.g.
If desired, it can also be combined with a photosensitive layer, as disclosed in Nos. 3,362,821 and 3,573,043. U.S. Pat. No. 3,594,164 and U.S. Pat.
In film units, such as those disclosed in US Pat. No. 3,594,165, these can also be placed on the spreader sheet used to aid in the application of processing liquids. As is currently well known and exemplified, for example, in the above-cited patents, liquid processing compositions used in the practice of multicolor diffusion transfer processes include at least an aqueous solution of an alkaline substance, such as sodium hydroxide, and preferably has a PH of greater than 12 and contains a thickening compound that constitutes a type of film-forming material that forms a relatively stiff and relatively stable film when the treatment composition is spread and dried. Most preferred. Representative film-forming materials include cellulosic polymers such as hydroxyethyl cellulose, sodium carboxymethyl cellulose and carboxymethyl hydroxyethyl cellulose; and oxime polymers such as polydiacetone acrylamide oxime. Other film-forming substances or thickeners with thickening capabilities that have substantially no effect when present in solution for extended periods of time may also be used. The film-forming material has a viscosity greater than 100 cps at a temperature of about 24°C, preferably at a temperature of about 24°C.
It is preferable to include it in the treatment composition in an amount suitable for imparting a viscosity on the order of 100,000 cps to 200,000 cps. In a particularly useful embodiment, the transparent polymeric support contains a small amount of a pigment, such as carbon black, which allows the pigment to exit by internal reflection within the transparent support and from the surface of the support carrying subsequent photographic layers. It is possible to prevent fog from occurring due to light piping of the active incident light hitting the edge. Such elements are covered by Belgian patent no.
Disclosed in No. 777407. It may be advantageous if the transparent support contains a UV absorber. For the purpose of illustrating the invention, a polyoxyethylene polymer layer containing the compound of Example 1 was grafted onto hydroxyethylcellulose (HEC).
- Vinylpyridine (4VP) and vinylbenzyltrimethylammonium chloride (TMQ)
A 2:1 mixture of graft copolymer and gelatin in a HEC/4VP/TMQ ratio of 2.2/2.2/1 is coated onto an image receiving layer supported on a clear 4 mil polyethylene terephthalate film base. . Applying a few drops of 1N KOH aqueous solution on this layer will result in
The compound of Example 1 was decolorized. 0.25N containing 30% acetonitrile as a solvent for the half-life of compounds A to D below.
It was measured using a KOH aqueous solution at 22°C using a spectrophotometer in a conventional manner. The term "half-life" refers to the time required for half of the compound to undergo alkaline hydrolysis according to the following reaction equation: The results obtained are shown in a table, where Y represents a substituent ortho to the benzoylsulfonamide group.

[Table] Figure 3 shows the Hammett plot for the data shown in the table above, and shows the equation
It is based on 10gK′ _x /K′ _o = α〓. As can be seen with reference to the data in the table and with reference to the Hammett plot, the rate of hydrolysis increases the more electron-withdrawing X is. From the half-life expressed as T1/2, the preferred compound of the present invention is 0.25N KOH
Decolorization occurs in about 30 seconds or less as measured in solution, ie, half of the colored compound undergoes alkaline hydrolysis in about 30 seconds or less. It will be appreciated that in using the dyes of this invention, a wide variety of solvents can be used to disperse the dyes in the appropriate layers of the photographic product, and useful solvents can be readily selected for a given compound. It can also be placed outside the silver halide emulsion layer (single or multilayer) when the anion may have a detrimental effect on the photosensitive material, and also because of the mobility of the dye in the specified matrix or binder. Depending on the situation, immobilizing group(s) may be used to fix the dye in the matrix to prevent migration of the dye, especially if the photographic product is exposed to high temperature and humidity conditions prior to use. It will be appreciated that this may be desirable. It is also possible to use the dyes of the invention to correct color balance, for example in a multicolor diffusion transfer film unit, to expose a photosensitive element to a suitable multicolor step-wedge and to transfer the diffusion transfer to a specified processing composition and receiver element. It is obvious that this can be done using
Blue, green and red D log E curves of the resulting multicolor transfer image (sample image) are then created. These D log E
Those who are familiar with color photographic sensitivity should check the curves for each D.
This is an example of how the log E curve deviates from the desired curve shape and to what extent. From this experiment,
Routine analysis and experimentation can further determine which wavelength range(s) and how much exposure is required to obtain the desired color balance. using another film unit photosensitive element having the same photosensitive element, image receiving element and processing composition to obtain a sample image;
The same exposure is carried out through a conventional color correction filter(s) of color and density estimated to be necessary to obtain the desired change in the D log E curve of the sample image. The blue, green, and red D log E curves of the resulting test multicolor transfer images are generated and compared to those of the sample images described above. Determining the most effective color filtration to obtain the desired D log E curve shape change may require more than one "test," but such tests can be performed quickly and easily.
Once a suitable color filtration has been determined, a layer containing color-correcting dye(s) that absorbs light in the desired wavelength range(s) may be added to achieve the required density. onto a transparent support with the calculated coverage. This "test" color correcting dye layer is placed in the exposure path and the exposure test described above is repeated. Analysis of the D log E curve of the resulting multicolor diffusion image reveals what, if any, changes should be made in the spectral absorption range and density before placing the corresponding color correcting dye layer in the diffusion transfer film unit. I understand. Exposure through a layer containing the dye(s) of the invention is effective for the "filter", i.e. the color correcting dye(s)
by the light absorbed by the species (or seeds or more)
The exposure given to the exposureable silver halide layer (single layer or multiple layers) is reduced and one or more dyes of the invention are added to each red, green to obtain the desired color balance. It will be appreciated that it can be used in combination with other filter dyes that produce changes in one, two or all three of the blue H and D curves. Although the dyes of the present invention have been found to be particularly useful in diffusion transfer and other photographic film units where it is desired to bleach the dye during processing after exposure through the dye layer (single layer or multiple layers), The dyes of this invention can also be used in diffusion transfer and other film units where the dye is present in locations where the dye concentration is not relevant to the transferred or final image. "Unbleached" is used when the filter dye layer through which the exposure is made is not part of the transferred image, or when the final image is masked from view, as in some integrated negative-positive reflective print constructions. The filter dye should be non-diffusible to the image-receiving layer containing the transferred image. The required non-diffusivity can be imparted by the use of suitable mordants, or by the use of long chain "ballast" or "anchor" substituents, and/or by other known techniques. The selection of the location of the color correcting dye(s) will depend in part on which stage of the manufacturing process the formulation of such color correcting dye is determined. As is readily apparent, the color correcting dye (1
The application of seeds (or seeds or more) has the advantage of allowing modification after the part has been sufficiently "aged", and of allowing portions of the same lot of positive parts to be modified differently. Supports for the various layers may be of any type known in the art to be useful. In preferred embodiments in which integrated negative-positive reflective prints are obtained, the support should be dimensionally stable and may be a polyethylene terephthalate or other polymeric film base, as disclosed in the above-cited patents. can be. After exposing and processing a film unit of the type illustrated in FIG. 2, the transferred image produced is a geometrically inverted image of the subject. Therefore, to obtain a geometric non-reversal image, such film-by-film exposure may be used as disclosed, for example, in U.S. Pat. No. 3,447,437 issued June 3, 1969 to Douglas B. Tiffany. It should be implemented through an image reversing system, such as in a camera with an image reversing system using a mirror lens, as shown in FIG. Where the expression "positive image" is used, this expression is primarily used for illustrative purposes and should not be construed in a limiting sense. That is, this is the concept of positive-negative, and is defined as an image formed on the image-receiving layer that is inverted with respect to the image of the light-sensitive emulsion layer. Another example of the meaning of "positive image" is:
It can be envisaged that the photosensitive element is exposed to actinic radiation through a negative transparency. In this case, the latent image in the light-sensitive emulsion layer is positive and the dye image formed on the image-receiving layer is negative. The expression "positive image" includes images produced in such image-bearing layers as well as transferred images obtained by directly using a positive silver halide emulsion to obtain a "positive" image of the subject. . Although the utility of the xanthene dyes of the present invention has been illustrated in the context of an integrated diffusion transfer film unit in which the transferred image is retained with the developed photosensitive element as part of a permanent laminate, the xanthene dyes of the present invention may Additionally, antihalation, color correction, or other light filtering layers (single layer or It will be appreciated that it can be used to apply a layer or multiple layers). Although the image dye-providing material is preferably a dye developer, it will be appreciated that other types of image dyes and dye intermediates can be used to form dye transfer images. In addition to their utility in diffusion transfer photographic products and methods, the xanthene dyes of the present invention can also be used in filter layers of common photographic materials, such as antihalation or color correction layers of common negative films, and They can be placed in a suitable layer (single layer or multilayer) in an amount sufficient to obtain the desired exposure effect. Selection and formulation of xanthene dyes to obtain the desired exposure effect can be accomplished in a known manner using conventional techniques and is within the skill of those skilled in the art. For example, for color correction purposes dyes (1
seeds or more) and place them in the layer through which the exposure is made. For certain cases, it may be desirable to filter light in two different wavelength ranges in such a ratio that one silver halide emulsion undergoes more exposure filtration than the other. That is certainly true. As in diffusion transfer film units, the dye(s) selected for color correction "matures" the photosensitive element.
It is advantageous to apply it after ripening to a point where the sensitometry of the photosensitive element produced no longer changes significantly over time. If the dyes of the invention are used for antihalation purposes, they can be incorporated, for example, in a layer on one or both sides of a support carrying a photosensitive layer (single or multilayer); When using dyes as optical filter agents, they can be used during processing in room light, without of course interfering with the imagewise exposure of the light-sensitive layer (single or multilayer).
or the final image can be seen with the naked eye to prevent fog from occurring due to post-exposure. All matter contained in the foregoing description and examples shall be explained as certain modifications may be made to the subject matter defined in the claims without departing from the scope of the invention encompassed herein. should be construed and is not intended to be limiting.

[Brief explanation of the drawing]

1 and 2 are schematic enlarged cross-sectional views of a diffusion transfer film unit incorporating the xanthene dyes of the present invention as a bleachable antihalation dye layer and as a color correcting filter dye in the image receiving layer, respectively; FIG. 3 is a graph based on the Hammett equation showing that the change in the Hammett sigma value regarding the substituent X of the xanthene compound of the present invention has a linear relationship with the hydrolysis rate.

Claims (1)

[Scope of Claims] 1. A photographic product comprising a plurality of layers including a support and at least one light-sensitive silver halide emulsion layer supported on the support, the photographic product comprising: a support and at least one light-sensitive silver halide emulsion layer supported on the support; At least one layer in the expression [In the formula, each R ¹ is the same and selected from [Formula] and [Formula]; R ² is alkyl, and R ³ is an electron-withdrawing group in the ortho, meta or para position to the N atom. and R ⁴ is hydrogen, alkyl or N
an electron-withdrawing group in the ortho, meta or para position to the atom; R ⁵ is alkyl;
is hydrogen, an electron-withdrawing group, or an electron-donating group; and A is an anion. 2. A photographic product according to claim 1, wherein the coloring compound is located in a processing composition permeable layer on the same side of the support as the silver halide emulsion layer (single or multilayer). 3. A photographic product according to claim 2, comprising, in order, a support, a light-sensitive silver halide emulsion layer and a layer containing a coloring compound. 4 supported on the support or a second support and arranged to receive a silver diffusion transfer image upon application of an aqueous alkaline processing composition to provide a silver halide developer and a silver halide solvent; 4. A photographic product according to claim 3, comprising a silver precipitated layer. 5. Claim 4 comprising, in order, a support, an additive multicolor screen, a silver precipitation layer, a silver halide emulsion layer and a layer of a colored compound, wherein the support is transparent.
Section photo products. 6. Photographic product according to claim 2, wherein the support is transparent and the colored compound is dispersed in a layer between the support and the silver halide emulsion layer (single or multilayer). 7. The photographic product of claim 2 further comprising, on the opposite side of the support, a layer of a colored compound coated on the light-sensitive silver halide emulsion layer furthest from the support. 8. Claim 2, wherein the silver halide emulsion layer is a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer having a combination of dye image-providing substances. Section photo products. 9. A photographic product for forming multicolor diffusion transfer images,
It carries a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, and these emulsion layers each contain a cyan image dye-providing material, a magenta image dye-providing material, and a blue-sensitive silver halide emulsion layer. having in combination a yellow image dye-providing substance;
a first sheet-like element having a first support; a second sheet-like element having a second support; a rupturable container for releasably retaining the aqueous alkaline treatment composition; an image receiving layer carried by one of said two supports; and a colored xanthene compound disposed within a processing composition permeable layer carried by one of said two supports; and the second sheet-like element are in a stacked relationship with the two supports as the outermost layers,
or suitable for stacking, at least one of the two supports being transparent;
Exposure of the silver halide emulsion is possible through one of the transparent supports, and the rupturable container is arranged to release the processing composition between a pair of defined layers carried by the two supports. and the above xanthene compound has the formula [In the formula, each R ¹ is the same and selected from the groups [Formula] and [Formula], R ² is alkyl, and R ³ is an electron-withdrawing group in the ortho, meta, or para position to the N atom. and R ⁴ is hydrogen, alkyl or N
is an electron-withdrawing group in the ortho, meta or para position relative to the atom, R ⁵ is alkyl, and X
is hydrogen, an electron-withdrawing group or an electron-donating group, and A is an anion. 10. The photographic product of claim 9, wherein the colored compound is arranged such that exposure of the silver halide emulsion layer takes place through said colored compound. 11. The photographic product of claim 10, wherein the second support is transparent and the image-receiving layer and the optical screening dye are carried by the transparent second support of the second sheet-like element. 12. The photographic product of claim 9, wherein the product includes means for providing a layer of white pigment between the image-receiving layer and the silver halide emulsion layer. 13. The photographic product of claim 12, wherein the means for providing a layer of white pigment comprises a white pigment dispersed in the processing composition. 14. The photographic product of claim 12, wherein the means for providing a layer of white pigment comprises a preformed layer of white pigment. 15. The photographic product of claim 11, wherein the colored compound is arranged in a layer above the image-receiving layer. 16. Claim 14, wherein the colored compound is arranged in a preformed layer of white pigment.
Section photo products. 17. The photographic product of claim 9, wherein each image dye-providing material is an image dye-providing material selected from image dyes and image dye intermediates. 18. The photographic product of claim 17, wherein the image dye-providing substance is a dye. 19. The photographic product of claim 18, wherein the dye is a dye developer. 20. The photographic product of claim 9, wherein the first sheet-like element and the second sheet-like element are in a stacked relationship. 21 Claim 9, wherein the second sheet-like element is suitable for stacking with the first sheet-like element
Section photo products. 22. The photographic product of claim 11, wherein the first support is opaque. 23. The photographic product of claim 10, wherein the first support and the second support are transparent. 24 comprising at least one light-sensitive silver halide emulsion layer supported on a support, and at least one layer on the support having the formula [In the formula, each R ¹ is the same and is selected from [Formula] and [Formula], R ² is alkyl, and R ³ is an electron-withdrawing group in the ortho, meta or para position with respect to the N atom. and R ⁴ is hydrogen, alkyl or N
is an electron-withdrawing group in the ortho, meta or para position relative to the atom, R ⁵ is alkyl, and X
is hydrogen, an electron-withdrawing group or an electron-donating group, and A is an anion. Emulsion layer (single layer or multilayer) with alkaline PH
1. A photographic method comprising the step of contacting and developing an aqueous alkaline processing composition having an aqueous alkaline processing composition. 25 The colored compound is disposed in a processing composition permeable layer on the same side of the support as the silver halide emulsion layer, and the pH of the processing composition in contact with the colored compound is
Based on 25. The photographic method of claim 24, wherein the pH is maintained at an alkaline pH for a period sufficient to cause cleavage of the colored compound and conversion of the colored compound to a colorless closed ring compound. 26 The support is transparent, and the colored compound is mixed with the support and a silver halide emulsion layer (single layer or multilayer).
Claim 2 disposed in a layer between
Section 5 Photography method. 27. The photographic method of claim 25, wherein the film includes a layer of a colored compound coated on the silver halide emulsion layer furthest from the support on the opposite side of the support. 28 The silver halide emulsion layers are a red-sensitive silver halide layer, a green-sensitive silver halide layer and a blue-sensitive silver halide layer, and each emulsion layer has a combination of image dye-providing substances. 2
Section 5 Photography method. 29 Development and base 26. The photographic method of claim 25 including the step of separating the processing composition from contact with the film unit after irreversible cleavage of the film unit. 30 (a) a support carrying at least one light-sensitive silver halide emulsion layer having in combination an image dye-providing substance, an image-receiving layer suitable for receiving the solubilized image dye-providing substance diffused therein; [In the formula, each R ¹ is the same and selected from the groups [Formula] and [Formula], R ² is alkyl, and R ³ is an electron-withdrawing group in the ortho, meta, or para position to the N atom. R ⁴ is hydrogen, alkyl or an electron-withdrawing group in the ortho, meta or para position to the N atom, R ⁵ is alkyl and X is hydrogen, an electron-withdrawing group or an electron-donating group and A is an anion. (b) contacting the silver halide layer (single layer or multiple layers) and a coloring compound with a processing composition of alkaline PH; (c) exposing the silver halide layer (single layer or multiple layers) to light; ) thus developing; (d) the pH of the processing composition in contact with the colored compound;
Based on (e) forming an imagewise distribution of the diffusible image-providing material as a result of development; and (f) at least one imagewise distribution of the diffusible image-providing substance.
A photographic method comprising the combination of: transferring the part by diffusion to a layer suitable for receiving the material and producing a transferred image thereon. 31. The photographic method according to claim 30, which includes the step of holding the film units together after processing. 32 The processing composition contains a silver halide solvent,
and claim 31, wherein the transferred image is a silver image.
Section photo method. 33 The photosensitive film units are sequentially arranged on a transparent support,
Additive multicolor screen, image-receiving layer containing a silver precipitate layer,
33. The photographic method of claim 32, comprising a light-sensitive silver halide emulsion layer and a layer of a colored compound. 34 A photographic method for forming a multicolor diffusion transfer image, comprising: (a) carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer; a first sheet-like element having a first support in which each of these emulsion layers has a combination of a cyan image dye-providing material, a magenta image dye-providing material and a yellow image dye-providing material; a second sheet having a second support; a rupturable container holding the aqueous alkaline processing composition in a releasable state; an image-receiving layer carried by one of the two supports; and by one of the two supports. a colored xanthene compound disposed within the supported treatment composition permeable layer;
The sheet-like element and the second sheet-like element are in a stacked relationship with the two supports as the outermost layer, or are suitable to be in a stacked relationship, and at least one of the two supports is It is transparent;
The silver halide emulsion layer can be exposed through one of the transparent supports, and the rupturable container can release the processing composition between a pair of defined layers carried by the two supports. and the above xanthene compound has the formula [In the formula, each R ¹ is the same and selected from the groups [Formula] and [Formula], R ² is alkyl, and R ³ is an electron-withdrawing group in the ortho, meta, or para position to the N atom. R ⁴ is hydrogen, alkyl or an electron-withdrawing group in the ortho, meta or para position to the N atom, R ⁵ is alkyl and X is hydrogen, an electron-withdrawing group or an electron-donating group and A is an anion], and the group (b) exposing the photosensitive film unit in which the group undergoes an irreversible cleavage reaction with a base that is completed within a predetermined time at a predetermined alkaline PH; (c) thus the silver halide layer (single or multilayer);
(d) the pH of the processing composition in contact with the colored compound;
Based on (e) forming an imagewise distribution of the diffusible image-providing material as a result of development; and (f) at least one imagewise distribution of the diffusible image-providing substance.
A photographic method comprising the steps of: transferring the part by diffusion to a layer suitable for receiving the material, producing a transferred image thereon. 35. Claim 3, wherein the layer containing the colored compound is arranged such that the exposure of the silver halide layer (single or multilayer) is carried out therethrough.
Section 4: Photography method. 36. Claim 35, wherein the second support is transparent, and the image-receiving layer and the colored compound are carried by the transparent second support of the second sheet-like element.
Section photo method. 37. The photographic method of claim 35, wherein the product includes means for providing a layer of white pigment between the image-receiving layer and the silver halide emulsion. 38. The photographic method of claim 37, wherein the means for providing a layer of white pigment comprises a white pigment dispersed in the processing composition. 39. The photographic method of claim 37, wherein the means for providing a layer of white pigment comprises a preformed layer of white pigment. 40. The photographic method of claim 36, wherein the optical screening dye is disposed in the image receiving layer. 41. The photographic method of claim 34, wherein each image dye-providing material is an image dye-providing material selected from image dyes and image dye intermediates. 42. The photographic method of claim 41, wherein each image dye-providing substance is a dye. 43. The photographic method of claim 42, wherein each dye is a dye developer. 44. The photographic method of claim 34, wherein the first sheet-like element and the second sheet-like element are in a stacked relationship. 45 Claim 3 in which the second sheet-like element is suitable for stacking with the first sheet-like element
Section 4: Photography method. 46. The photographic method of claim 36, wherein the first support is opaque.